CN100580974C - Organic EL device and its efficient improving method - Google Patents

Organic EL device and its efficient improving method Download PDF

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CN100580974C
CN100580974C CN200610071445A CN200610071445A CN100580974C CN 100580974 C CN100580974 C CN 100580974C CN 200610071445 A CN200610071445 A CN 200610071445A CN 200610071445 A CN200610071445 A CN 200610071445A CN 100580974 C CN100580974 C CN 100580974C
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source
hole
electron source
electroluminescent device
layer
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CN1845356A (en
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刘醕炘
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Optoelectronic Science Co ltd
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AU Optronics Corp
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H10K50/171—Electron injection layers

Abstract

An OLED comprises an anode, a hole source, an emissive region, an electron source and a cathode, wherein the materials for the electron source and the hole source are chosen such that the electrical conductivity of these charge carrier sources is greater than the electrical conductivity of the emissive region. In particular, the electrical conductivity of the source layers is between 10<SUP>-8 </SUP>to 10<SUP>2 </SUP>S/cm. Furthermore, one or both of the hole source and the electron source are made substantially of one or more inorganic materials. The emissive region can have one or more layers of organic material. The materials for the emissive region are insulators. The cathode can be made of a metal such as Mg:Ag and Al, and the anode is made of ITO or the like. The electrical conductivity of the cathode and the anode is significantly higher than 10<SUP>2 </SUP>S/cm.

Description

Organnic electroluminescent device and promote the method for its efficient
Technical field
The present invention relates to a kind of electrooptical device, further, relate to a kind of Organnic electroluminescent device.
Background technology
(organic light-emitting device OLED) is the hot technology field of widely being studied at present to Organnic electroluminescent device.At United States Patent (USP) the 5th, 776, in No. 623, disclosed a kind of electroluminescent device (electroluminescent device), this electroluminescent device uses the cyanine copper (copper-phthalocyanine of 15 nanometer thickness, hereinafter to be referred as CuPc) as hole injection layer (hole injection layer, HIL), the N of 60 nanometer thickness, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4,4 ' (N, N '-bis-(1-naphthyl)-N, N '-diphenyl-1,1 '-biphenyl-4,4 '; Hereinafter to be referred as NPB) as hole transmission layer (hole transport layer, HTL), 8-hydroxyl quinoline aluminium salt (tris (8-hydroxyquinoline) aluminum of 75 nanometer thickness; Be Alq 3) as electron transfer layer (electron transportlayer, ETL); Then at Alq 3The lithium fluoride of last deposition 0.5 nanometer thickness, this lithium fluoride can use following material substitution: magnesium fluoride, calcirm-fluoride, lithia or magnesium oxide.
At United States Patent (USP) the 6th, 013, in No. 384, disclosed a kind of organic electroluminescent device, as shown in Figure 1a, this organic electroluminescent device 10 is make to form on substrate 11, and anode 12, hole transmission layer 13, luminescent layer 14, the organic compound layer 15 that is doped with metal then are formed on the substrate 11 in regular turn with negative electrode 16.Comprise the organic layer 17 that is formed between anode 12 and the negative electrode 16 in the organic electroluminescent device 10, comprise hole transmission layer 13, luminescent layer 14 and the organic compound layer 15 that is doped with metal in this organic layer 17.
In U.S. Patent Publication No. 2004/0032206A1, disclosed the another kind of Organnic electroluminescent device that comprises alkali halide, shown in Fig. 1 b, this Organnic electroluminescent device 20 is to make to form on plastic base 21, and anode 22, hole transmission layer 23, luminescent layer 24, electron transfer layer 25, alkali compound layer 26 then are formed on the substrate 21 with negative electrode 27 in regular turn; Wherein, this plastic base 21 is coated with ito anode 22 in advance.Negative electrode 27 by metal oxide layer 27b with contain magnesium layer 27a and constitute, can constitute by magnesium or magnesium alloy (for example magnesium silver alloy) and contain magnesium layer 27a.Alkali compound layer 26 can be by alkali halide (for example LiF) or alkali metal oxide (Li-for example 20) constitutes.Organic layer 28 comprises hole transmission layer 23, luminescent layer 24 and electron transfer layer 25.
At United States Patent (USP) the 6th, 551, in 725B2 number, disclosed a kind of Organnic electroluminescent device, Organnic electroluminescent device 30 shown in Fig. 1 c is to be formed on the substrate 31, and anode 32, hole injection layer 33, hole transmission layer 34, luminescent layer 35, electron transfer layer 36, buffer structure 37 then are formed on the substrate 31 with negative electrode 38 in regular turn; This Organnic electroluminescent device 30 comprises a buffer structure 37, is formed between organic layer 39 and the negative electrode 38.This buffer structure 37 comprises the first resilient coating 37a and the second resilient coating 37b, the first resilient coating 37a is made of alkali halide, be formed on the electron transfer layer 36, and the second resilient coating 37b is made of the metal or metal alloy of work function between 2.0-4.0 electron-volt (eV), is formed on the first resilient coating 37a.Except that this, hole injection layer 33 is to be formed between anode 32 and the organic layer 39.Hole injection layer 33 can be made of pyrroles's sclererythrin (porphorinic) or cyanine (phthalocyanine), also can be by carbon fluorine macromolecule CF xConstitute, wherein x is 1 or 2.Hole transmission layer 34 can be made of various different types of aromatic amines (aromatic amines).In luminescent layer 35,, thereby can launch light because compound (recombination) carried out at this in electronics and hole.Negative electrode 38 uses sputtering sedimentation (sputter deposition) modes to form, in order to higher conductance (conductivity) of this Organnic electroluminescent device 30 and albedo preferably to be provided.
General Organnic electroluminescent device then as shown in Figure 2, Organnic electroluminescent device 40 is to be formed on the substrate 41, and anode 42, source, hole 43, luminescent layer 44, electron source 45, first resilient coating 46, second resilient coating 47 then are formed on the substrate 41 with negative electrode 48 in regular turn; Wherein, hole injection layer 43a and hole transmission layer 43b constitute source, hole 43 jointly; Electron injecting layer 45b and electron transfer layer 45a constitute electron source 45 jointly.Source, hole 43 and/or electron source 45 can be made of organic material or inorganic material.Luminescent layer 44 is made of the organic main body (organic host) that is doped with fluorescence (fluorescent) alloy or phosphorescence (phosphorescent) alloy.In general, the conductance in traditional electrical component or source, hole is less than 10 -8Therefore S/cm has limited the luminous efficiency of general Organnic electroluminescent device 40.
Traditional Organnic electroluminescent device 40 as shown in Figure 2 is except anode 42 is that (conductance is more than or equal to 10 for high conductivity with negative electrode 48 2S/cm) outside the material, the organic material between two electrodes is the extremely low insulator of conductance, and (conductance is less than 10 -8S/cm), therefore, the conductivity distribution of traditional Organnic electroluminescent device 40 inside is: high (anode) → low (organic layer) → height (negative electrode).Because electrode and organic layer conductance drop at the interface are too big, therefore, electrode and organic layer tire easily accumulated charge at the interface inject energy barrier so that can produce a large amount of Joule heats at the interface and form high carrier, this phenomenon can cause the assembly instability, and causes high operating voltage.
In addition, because operating voltage is too high, therefore traditional Organnic electroluminescent device must be limited in structural thickness the interior too high to prevent operating voltage of specific thickness, but thin excessively structural thickness often makes the less stable of assembly.For example, because anode ITO generally adopts the mode of sputter (sputter) to make, so its surface has sharp-pointed crystallization (spike) easily, at this moment, if the thickness low LCL of organic layer is thick, then sharp-pointed ITO pierces through organic membrane easily and causes short circuit.In addition, when making active panel, owing to connect thin-film transistor (the Thin Film Transistor of ito anode, TFT) when running, can produce high heat, and the neither height of fusing point (about about 100-200 ℃) of general organic material, so when organic layer was too thin, light-emitting zone can be subjected to serious heat interference and influence luminous efficiency.
Summary of the invention
Mirror is arranged at this, the present invention mainly provides a kind of Organnic electroluminescent device, and the method that promotes Organnic electroluminescent device efficient, can the conductance of those materials be reached greatly than the conductance of luminous zone via the material of selecting electron source and source, hole.The conductance in electron source and source, hole is preferably between 10 -8To 10 2Between the S/cm.
Further, in one embodiment of the invention, utilize conductivity distribution to change following form into: high (more than or equal to 10 with Organnic electroluminescent device 2S/cm) → in (between 10 -8To 10 2S/cm) → low (less than 10 -8S/cm) → in (between 10 -8To 10 2S/cm) → high (more than or equal to 10 2S/cm), the conductivity distribution that replaces traditional Organnic electroluminescent device: high (greater than 10 2S/cm) → low (less than 10 -8S/cm) → high (greater than 10 2S/cm), in order to improve shortcomings such as traditional Organnic electroluminescent device operating voltage height and poor stability.And implementation method is via between the organic layer of the electrode of high conductivity and low conductivity, forms one or more layers and has the moderate conductance (between 10 -8To 10 2S/cm) semimetal (semi-metal) material, because semi-metallic has the conductance that is higher than about 5 progression of organic material (10,000 times), so it is also little to the influence of the operating voltage of Organnic electroluminescent device to increase the thickness of semimetal layer, therefore, can utilize this characteristic to thicken the thickness of semimetal layer, to make good Organnic electroluminescent device, make its assembly, low operating voltage, have good hot-fluid resilient coating with high stability, and the influence that reduces the sharp-pointed crystallization (spike) in surface of ito anode.
In addition, because in one embodiment of the invention, with the conductivity distribution of Organnic electroluminescent device be adjusted into height → in → low → in → height, therefore, the conductance drop at each place, bed boundary of Organnic electroluminescent device is comparatively gentle, can reach and reduce the purpose that carrier injects energy barrier and reduces Joule heat at the interface, be very helpful for the stable tool of the assembly of Organnic electroluminescent device.
A kind of Organnic electroluminescent device is provided in one embodiment of the invention, includes negative electrode, anode and layer structure, this layer structure is formed between negative electrode and the anode, and layer structure includes source, hole, electron source and luminous zone; The source, hole is in close proximity to anode; Electron source is in close proximity to negative electrode; The luminous zone is formed between source, hole and the electron source, and the luminous zone can be made of organic material, and this organic material contains alloy, and source, above-mentioned hole, electron source and luminous zone have conductance separately respectively, and wherein, the conductance in source, hole is between 10 -8To 10 2Between the S/cm; The conductance of electron source is between 10 -8To 10 2Between the S/cm; The conductance of luminous zone is less than 10 -8S/cm; The conductance of negative electrode and this anode is more than or equal to 10 2S/cm, wherein electron source and/or source, hole comprise inorganic material.
A kind of method that promotes Organnic electroluminescent device efficient is provided in another embodiment of the present invention, comprises: Organnic electroluminescent device is provided, and in the hole source material with this Organnic electroluminescent device of iontophoresis, the conductance that makes the source, hole is between 10 -8To 10 2Between the S/cm; And in the electron source material with this Organnic electroluminescent device of iontophoresis, the conductance that makes electron source is between 10 -8To 10 2Between the S/cm; Wherein, the conductance of luminous zone is less than the conductance of source, hole and electron source, and the conductance of negative electrode and anode is greater than the conductance of source, hole and electron source.Above-mentioned Organnic electroluminescent device includes negative electrode, anode and layer structure, and this layer structure is formed between negative electrode and the anode, and layer structure includes source, hole, electron source and luminous zone; The source, hole is in close proximity to anode, and the source, hole is made of the hole source material; Electron source is in close proximity to negative electrode, and electron source is made of electron source material, and wherein hole source material and/or electron source material comprise inorganic material; The luminous zone is formed between source, hole and the electron source, and the luminous zone is made of organic material, and this organic material contains alloy, and source, hole, electron source and luminous zone have conductance separately respectively.
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, preferred embodiment cited below particularly, and cooperate appended graphicly, be described in detail below:
Description of drawings
Fig. 1 a-1c and Fig. 2 are the comparative examples that traditional Organnic electroluminescent device is shown.
Fig. 3 is the conductance graph of a relation according to the different layerings of the Organnic electroluminescent device shown in the embodiment of the invention.
Fig. 4 a-4c, Fig. 5 a-5c, Fig. 6-7, Fig. 8 a-8c, Fig. 9 a-9c, Figure 10 a-10c and Figure 11-the 12nd, the Organnic electroluminescent device shown in the different embodiment according to the subject invention.
[primary clustering symbol description]
13,23,34,43b～hole transmission layer;
15～be doped with the organic compound layer of metal;
17,28,39～organic layer;
21～plastic base;
25,36,45a～electron transfer layer;
26～alkali compound layer;
27a～contain magnesium layer;
27b～metal oxide layer;
33,43a～hole injection layer;
37～buffer structure;
37a, 46～the first resilient coatings;
37b, 47～the second resilient coatings;
45b～electron injecting layer;
10,20,30,40,400a, 400b, 400c, 500a, 500b, 500c, 600,700,800a, 800b, 800c, 900a, 900b, 900c, 1000a, 1000b, 1000c, 1100,1200～Organnic electroluminescent device;
11,31,41,401,501,601,701,801,901,1001,1101,1201～substrate;
12,22,32,42,402,502,602,702,802,902,1002,1102,1202～anode;
43,403,503,603,703,803a, 803b, 803c, 903,1003,1103, source, 1203～hole;
14,24,35,44,404,504,604,704,804,904,1004,1104,1204～luminous zone;
45,405,505,605,705,805a, 805b, 805c, 905,1005,1105,1205～electron source;
16,27,38,48,406,506,606,706,806,906,1006,1106,1206～negative electrode;
405a, 405c, 705a～first electron source;
405b, 405d, 705b～second electron source;
503a, 503c, 703a～source, first hole;
503b, 503d, 703b～source, second hole;
806a, 906a, 1006a, 1106a～aluminium electrode;
806b, 906b, 1006b, 1106b～electron injecting layer;
905a, 905c, 1105a, 1205a～first electron transfer layer;
905b, 905d, 1105b, 1205b～second electron transfer layer;
1003a, 1003c, 1103a, 1203a～first hole injection layer;
1003b, 1003d, 1103b, 1203b～second hole injection layer;
804a, 904a, 1004a, 1104a, 1204a～N-type resilient coating;
804b, 904b, 1004b, 1104b, 1204b～luminescent layer;
804c, 904c, 1004c, 1104c, 1204c～P-type resilient coating.
Embodiment
PIN diode (Positive-Intrinsic-Negative diode) is a kind of photodiode (photodiode), this photodiode has roomy (large) and the essence district (intrinsic regior) of neutral (neutrally) material that mixes, and the essence district is between P type doped region and N type doped region.Dopant in P type doped region and the N type doped region has increased the conductance of semi-conducting material in this doped region significantly, and has promoted device usefulness.
In the Organnic electroluminescent device of one embodiment of the invention, comprise negative electrode, electron source, luminescent layer, source, hole and anode.The employed material of above-mentioned electron source and source, hole is to adopt conductance greater than luminescent layer but less than the material of negative electrode and anode.Shown in the 3rd figure, the conductance of luminous zone is less than 10 -8S/cm, the electricity in the source and the conductance in source, hole then between 10 -8To 10 2Between the S/cm.Basically the conductance of negative electrode and anode is more than or equal to 10 2S/cm constitutes if negative electrode is a metal by for example silver or aluminium, and then its conductance can be higher than 10 6S/cm; If anode is that (Indium Tin Oxide ITO) constitutes, and then its conductance can be between 10 by indium tin oxide 3To 5*10 3Between the S/cm.
In the Organnic electroluminescent device of another embodiment of the present invention, electron source and/or source, hole are to be made of inorganic material, and this inorganic material has greater than 10 -8The conductance of S/cm.Fig. 4 a-4c is Organnic electroluminescent device 400a, 400b and the 400c shown in the Shu embodiment according to the present invention, has substrate 401, and anode 402, source, hole 403, luminous zone 404, electron source 405 then are formed on the substrate 401 with negative electrode 406 in regular turn; Wherein, source, hole 403 is to be made of organic material, and the conductance of luminous zone 404 is less than 10 -8S/cm, the conductance of source, hole 403 and electron source 405 is then greater than 10 -8S/cm.Organnic electroluminescent device 400a, 400b and 400c in one embodiment of the present of invention have negative electrode 406, and this negative electrode 406 can be made of unitary electrode, perhaps constituting by electrode and electronics injection material.Electron source 405 can be by the single layer structure of same material, or is made of the sandwich construction of different materials.Shown in Fig. 4 a, electron source 405 can be made of the individual layer inorganic material; Perhaps shown in Fig. 4 b, electron source 405 is made of sandwich construction, and wherein, the first electron source 405a can be inorganic material, and the second electron source 405b can be organic material; Perhaps shown in Fig. 4 c, the first electron source 405c can be organic material, and the second electron source 405d can be inorganic material.
Fig. 5 a-5c is according to Organnic electroluminescent device 500a, 500b and the 500c shown in another embodiment of the present invention, has substrate 501, and anode 502, source, hole 503, luminous zone 504, electron source 505 then are formed on the substrate 501 with negative electrode 506 in regular turn; Wherein, electron source 505 is to be made of organic material, and source, hole 503 then can be made of inorganic material or organic material.Shown in 5a figure, source, hole 503 can be made of the individual layer inorganic material; Perhaps shown in 5b figure, source, hole 503 is made of sandwich construction, and wherein, first hole source 503a can be inorganic material, and second hole source 503b can be organic material; Perhaps shown in 5c figure, first hole source 503c can be organic material, and second hole source 503d can be inorganic material.
Fig. 6 is according to the Organnic electroluminescent device shown in another embodiment of the present invention 600, has substrate 601, and anode 602, source, hole 603, luminous zone 604, electron source 605 then are formed on the substrate 601 with negative electrode 606 in regular turn; Wherein, electron source 605 all is made of inorganic material with source, hole 603.
Fig. 7 is according to the Organnic electroluminescent device shown in another embodiment of the present invention 700, has substrate 701, and anode 702, source, hole 703, luminous zone 704, electron source 705 then are formed on the substrate 701 with negative electrode 706 in regular turn; Wherein, electron source 705 all is made of sandwich construction with source, hole 703, and each layering (sub-layer) 705a, 705b, 703a or the 703b in electron source 705 and source, hole 703 can be made of inorganic material or organic material respectively.
In order to increase the conductance in each electron source and source, hole, can use semimetal (semi-metal) to reach this purpose as the material in each electron source and source, hole.For example, contain the inorganic material of ion additive (ion-intercalated), perhaps contain the organic material of ion doping thing (ion-doped), be used as the material in electron source and source, hole, can reach 10 -6S/cm or higher conductance.
Fig. 8 a-8c is according to Organnic electroluminescent device 800a, 800b and the 800c shown in another embodiment of the present invention, has substrate 801, and anode 802, source, hole 803a, 803b or 803c, luminous zone 804, electron source 805a, 806 on 805b or 805c and negative electrode are formed on the substrate 801 in regular turn.Please refer to 8a figure, in one embodiment of the invention, electron source 805a is made of the inorganic material that contains the ion additive (N-type semimetal), and source, hole 803a is made of the organic material that contains the ion doping thing (P-type semimetal), and luminous zone 804 is made of one or more organic material.Please refer to 8b figure, in another embodiment of the present invention, source, hole 803b is made of the inorganic material that contains the ion additive (P-type semimetal), and electron source 805b is made of the organic material that contains the ion doping thing (N-type semimetal), and luminous zone 804 is made of one or more organic material.Please refer to 8c figure, in another embodiment of the present invention, electron source 805c is made of the inorganic material that contains the ion additive (N-type semimetal), and source, hole 803c is made of the inorganic material that contains the ion additive (P-type semimetal), and luminous zone 804 is made of one or more organic material.
The above-mentioned inorganic material that contains the ion additive that is used in electron source can for example be alkali metal or the alkaline earth metal compound based on oxide (oxide-based).Can be defined the metal oxide formation of (characterized) by following chemical formula based on the inorganic compound of oxide:
A x(M yO z)
Wherein, x, y and z are respectively the positive integer greater than zero;
A is alkali metal or alkali earth metal;
M is selected from metal, transition metal and metal alloy; And
O is an oxygen atom.
The above-mentioned inorganic material that contains the ion additive is selected from following compounds: LiMn 2O 4, LiCoO 2, LiNbO 3, Li 2WO 4, Cs 2WO 4, CsMnO 4, CsVO 4, CsTi 6O1 3, MgTiO 3, MgWO 4, MgZrO 3With Li (Ni 0.8Co 0.2) O 2In above-claimed cpd, Li=lithium, Mn=manganese, O=oxygen, Co=cobalt, Nb=niobium, W=tungsten, Cs=caesium, V=vanadium, Ti=titanium, Mg=magnesium, Zr=zirconium, Ni=nickel.
Above-mentioned for being used in the inorganic material that contains the ion additive of electron source; And the inorganic material that contains the ion additive that is used in the source, hole can be an inorganic compound, and this inorganic compound can be made of the defined oxide of following chemical formula:
P x(M yO z)
Wherein, x, y and z are respectively the positive integer greater than zero;
P is a p-type alloy, and for example (tetrafluoro-tetracyano-quinodimethane is hereinafter to be referred as F for tetrafluoro four cyano quinone bismethane 4-TCNQ);
M is selected from metal, transition metal and metal alloy; And
O is an oxygen atom.
The organic material that contains the ion doping thing can be the amine (amine) that contains p-type alloy, and this kind contains the conductance of amine of p-type alloy approximately between 4*10 -7To 6*10 -6Between the S/cm, the conductance of organic material that does not contain the ion doping thing is then less than 10 -9S/cm (can be considered electrical insulator).The organic material that contains the ion doping thing also can be the organic material of elements doped lithium, and it has approximately between 2*10 -5To 5*10 -5Conductance between the S/cm.
Fig. 9-the 12nd is according to the Organnic electroluminescent device shown in the different embodiments of the invention.Source, hole 903 among Fig. 9 a-9c is to be made of organic material.Organnic electroluminescent device 900a shown in Fig. 9 a has substrate 901, and anode 902, source, hole 903, luminous zone 904, electron source 905 then are formed on the substrate 901 with negative electrode 906 in regular turn; Wherein, source, hole 903 is made of hole injection layer, and this hole injection layer is by being doped with F 4The cyanine copper (CuPc) of-TCNQ constitutes.F 4-TCNQ is a kind of p-type alloy, and is doped with F 4The CuPc of-TCNQ then constitutes p-type semimetal.905 of electron sources are by having LiMn 2O 4Electron transfer layer constitute this LiMn 2O 4Be a kind of inorganic material that contains the ion additive.Luminous zone 904 then comprises following three layerings: luminescent layer 904b (emissive layer, EML), N-type resilient coating 904a and P-type resilient coating 904c, wherein, N-type resilient coating 904a is formed between luminescent layer 904b and the electron source 905, and P-type resilient coating 904c then is formed between luminescent layer 904b and the source, hole 903.Luminescent layer 904b comprises an organic main body (organic host), and this organic main body is doped with the alloy that can glow; N-type resilient coating 904a is by 4,7-diphenyl-1, the 10-phenanthroline (4,7-diphenyl-1,10-phenan-throline is hereinafter to be referred as BPhen) constitute; P-type resilient coating 904c is by N, N '-two-(1-naphthyl)-N, and N '-diphenyl-1,1 '-biphenyl-4,4 ' (NPB) constitutes.N-type resilient coating 904a also can be used as the usefulness of electron transfer layer; And P-type resilient coating 904c also can be used as the usefulness of hole transmission layer.Negative electrode 906 comprises that (electron injection layer, EIL), this electron injecting layer 906b is made of the LiF thin layer for aluminium electrode 906a and electron injecting layer 906b.
Electron source 905 except shown in Fig. 9 a by the individual layer electron transfer layer constitute, electron source 905 also can be made of double-deck electron transfer layer; Organnic electroluminescent device 900b and 900c shown in Fig. 9 b-9c have substrate 901, and anode 902, source, hole 903, luminous zone 904, electron source 905 then are formed on the substrate 901 with negative electrode 906 in regular turn; Wherein, the electron source 905 shown in Fig. 9 b can be made of the first electron transfer layer 905a and the second electron transfer layer 905b respectively, and the electron source 905 shown in Fig. 9 c can be made of the first electron transfer layer 905c and the second electron transfer layer 905d respectively.Relativeness between each layer is as follows: shown in Fig. 9 b, the second electron transfer layer 905b is formed on the luminous zone 904, and the first electron transfer layer 905a is formed on the electron transfer layer 905b, and negative electrode 906 then is formed on the first electron transfer layer 905a; Shown in Fig. 9 c, the second electron transfer layer 905d is formed on the luminous zone 904, and the first electron transfer layer 905c is formed on the second electron transfer layer 905d, and negative electrode 906 then is formed on the first electron transfer layer 905c.Shown in Fig. 9 b, in one embodiment of the invention, the first electron transfer layer 905a is by LiMn 2O 4Constitute, and the second electron transfer layer 905b is made of BPhen:Li; Shown in Fig. 9 c, in another embodiment of the present invention, the first electron transfer layer 905c is made of BPhen:Li, and the second electron transfer layer 905d is by LiMn 2O 4Constitute; In above-mentioned two embodiment, negative electrode 906 can be made of Mg:Ag.Because the source, hole 903 among Fig. 9 b-9c and the composition and the function of luminous zone 904, identical with the composition and the function of source, hole 903 among the 9a figure and luminous zone 904, do not repeat them here.
Figure 10 a-10c is according to Organnic electroluminescent device 1000a, 1000b and the 1000c shown in another embodiment of the present invention, and wherein, electron source 1005 is to be made of organic material.Organnic electroluminescent device 1000a shown in Figure 10 a has substrate 1001, and anode 1002, source, hole 1003, luminous zone 1004, electron source 1005 then are formed on the substrate 1001 with negative electrode 1006 in regular turn; Electron source 1005 is an electron transfer layer, is made of BPhen:Cs.Luminous zone 1004 comprises following three layerings: luminescent layer 1004b, N-type resilient coating 1004a and P-type resilient coating 1004c, wherein, N-type resilient coating 1004a is formed between luminescent layer 1004b and the electron transfer layer 1005, and P-type resilient coating 1004c then is formed between luminescent layer 1004b and the hole injection layer 1003.Luminescent layer 1004b comprises organic main body, and this organic main body is doped with the alloy that can glow; N-type resilient coating 1004a is by 4,7-diphenyl-1, and 10-phenanthroline (BPhen) constitutes; P-type resilient coating 1004c is by N, N '-two-(1-naphthyl)-N, and N '-diphenyl-1,1 '-biphenyl-4,4 ' (NPB) constitutes.N-type resilient coating 1004a also can be used as the usefulness of electron transfer layer; And P-type resilient coating 1004c also can be used as the usefulness of hole transmission layer.In Figure 10 a, source, hole 1003 is a hole injection layer, by being doped with F 4--the tungsten oxide (WO of TCNQ 3) constitute.And negative electrode 1006 comprises aluminium electrode 1006a and electron injecting layer 1006b, and this electron injecting layer 1006b is made of the LiF thin layer.
In Figure 10 b-10c, negative electrode is made of Mg:Ag, and source, hole 1003 can be respectively by the first hole injection layer 1003a among Figure 10 b and the second hole injection layer 1003b, and perhaps the first hole injection layer 1003c among Figure 10 c and the second hole injection layer 1003d constitute.Organnic electroluminescent device 1000b and 1000c shown in Figure 10 b-10c have substrate 1001, and anode 1002, source, hole 1003, luminous zone 1004, electron source 1005 then are formed on the substrate 1001 with negative electrode 1006 in regular turn; Relativeness between each layer is as follows: in Figure 10 b, the second hole injection layer 1003b is formed on the anode 1002, the first hole injection layer 1003a is formed on the second hole injection layer 1003b, and luminous zone 1004 then is formed on the first hole injection layer 1003a; In Figure 10 c, the second hole injection layer 1003d is formed on the anode 1002, and the first hole injection layer 1003c is formed on the second hole injection layer 1003d, and luminous zone 1004 then is formed on the first hole injection layer 1003c.Shown in Figure 10 b, in one embodiment of the invention, the first hole injection layer 1003a is by NPB:F 4-TCNQ constitutes, and the second hole injection layer 1003b is by F 4-TCNQ:WO 3Constitute; Shown in Figure 10 c, in another embodiment of the present invention, the first hole injection layer 1003c is by F 4-TCNQ:WO 3Constitute, and the second hole injection layer 1003d is by NPB:F 4-TCNQ constitutes.The electron source 1005 among Figure 10 b-10c and the composition and the function of luminous zone 1004, identical with the composition and the function of electron source 1005 among Figure 10 a and luminous zone 1004, do not repeat them here.
Figure 11 is the Organnic electroluminescent device structure 1100 shown in according to one embodiment of present invention, has substrate 1101, and anode 1102, source, hole 1103, luminous zone 1104, electron source 1105 then are formed on the substrate 1101 with negative electrode 1106 in regular turn; Wherein, electron source 1105 all is made of inorganic material with source, hole 1103.Electron source 1105 is an electron transfer layer, by LiMn 2O 4Constitute, source, hole 1103 is a hole injection layer, by F 4-TCNQ:WO 3Constitute.Negative electrode 1106 comprises aluminium electrode 1106a and electron injecting layer 1106b, and this electron injecting layer 1106b is made of the LiF thin layer.The composition and the function of the luminous zone 1104 among Figure 11, identical with the composition and the function of luminous zone 904 among Fig. 9 a, do not repeat them here.
Figure 12 is the Organnic electroluminescent device structure 1200 shown in according to one embodiment of present invention, has substrate 1201, and anode 1202, source, hole 1203, luminous zone 1204, electron source 1205 then are formed on the substrate 1201 with negative electrode 1206 in regular turn; Wherein, negative electrode 1206 is made of Mg:Ag, and electron source 1205 respectively comprises an inorganic material and an organic material with source, hole 1203.In Figure 12, electron source 1205 is made of electron transfer layer 1205a and 1205b, and source, hole 1203 is made of hole injection layer 1203a and 1203b, and wherein, electron transfer layer 1205a or 1205b can be by BPhen:Li or LiMn 2O 4Constitute, and hole injection layer 1203a or 1203b can be by NPB:F 4-TCNQ or F 4-TCNQ:WO 3Constitute.In an embodiment of the present invention, the first electron transfer layer 1205a is made of BPhen:Li, and the second electron transfer layer 1205b is by LiMn 2O 4Constitute; And the first hole injection layer 1203a is by NPB:F 4-TCNQ constitutes, and the second hole injection layer 1203b is by F 4-TCNQ:WO 3Constitute.The composition and the function of the luminous zone 1204 among Figure 12, identical with the composition and the function of luminous zone 904 among Fig. 9 a, do not repeat them here.
Generally, the Organnic electroluminescent device structure comprises negative electrode, source, hole, luminous zone, electron source and anode, and the present invention improves the usefulness of Organnic electroluminescent device device via the conductance of adjusting source, hole, electron source and luminous zone.The conductance of layers of material size is as follows respectively: the conductance in electron source and source, hole is greater than the conductance of luminous zone, but less than the conductance of negative electrode and anode.The conductance in electron source and source, hole is preferably between 10 -8To 10 2S/cm.In addition, electron source and/or source, hole are made of one or more inorganic material basically.In addition, one or more layers resilient coating also can be formed between negative electrode and the anode, and above-mentioned resilient coating can be the part of luminous zone.
Mode via the conductance of source, above-mentioned adjustment hole, electron source and luminous zone can make Organnic electroluminescent device of the present invention have the following advantages:
1. what make electrode and organic layer is not easy stored charge at the interface, and therefore also be not easy to produce a large amount of Joule heats at the interface and inject energy barrier, and then improve the stability of assembly with high carrier, and the reduction operating voltage.
2. in one embodiment of the invention, via between the organic layer of the electrode of high conductivity and low conductivity, form have in the semi-metallic of conductance, can reduce the influence of the sharp-pointed crystallization (spike) in surface of ito anode, and can be used as good hot-fluid resilient coating, avoid light-emitting zone to be subjected to heat and disturb and influence luminous efficiency.
Though the present invention with the preferred embodiment explanation as above; but it is not in order to qualification the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; can change and modify, so protection scope of the present invention is as the criterion so that appended claims is desired.

Claims (10)

1. Organnic electroluminescent device comprises:
Negative electrode;
Anode; And
Layer structure is formed between this negative electrode and this anode, and this layer structure comprises:
The source, hole is in close proximity to this anode;
Electron source is in close proximity to this negative electrode; And
The luminous zone is formed between this source, hole and this electron source, and this luminous zone is made of the organic material that contains alloy, and this source, hole, electron source and luminous zone have conductance separately respectively, wherein:
The conductance in this source, hole is between 10 -8To 10 2Between the S/cm;
The conductance of this electron source is between 10 -8To 10 2Between the S/cm;
The conductance of this luminous zone is less than 10 -8S/cm; And
The conductance of this negative electrode and this anode is more than or equal to 10 2S/cm,
Wherein: (1) this source, hole is sandwich construction and comprises and contain NPB:F 4The layering of-TCNQ and contain F 4-TCNQ:WO 3Layering; Or
(2) this electron source is sandwich construction and comprises and contain LiMn 2O 4Layering and the layering that contains BPhen:Li; Or
(3) this source, hole is sandwich construction and comprises and contain NPB:F 4The layering of-TCNQ and contain F 4-TCNQ:WO 3Layering, and this electron source is sandwich construction and comprises and contain LiMn 2O 4Layering and the layering that contains BPhen:Li.
2. Organnic electroluminescent device as claimed in claim 1, wherein this source, hole comprises P-type semimetal, and this electron source comprises N-type semimetal, and this luminous zone then comprises conductance less than 10 -8The electrical insulator of S/cm.
3. Organnic electroluminescent device as claimed in claim 1, wherein this source, hole comprises the inorganic material that contains the ion additive, this electron source comprises the organic material that contains the ion doping thing.
4. Organnic electroluminescent device as claimed in claim 1, wherein this source, hole comprises the inorganic material that contains the ion additive, this electron source comprises the inorganic material that contains the ion additive.
5. Organnic electroluminescent device as claimed in claim 1, wherein this source, hole comprises the organic material that contains the ion doping thing, this electron source comprises the inorganic material that contains the ion additive.
6. Organnic electroluminescent device as claimed in claim 1, wherein this luminous zone comprises luminescent layer and P-type resilient coating, wherein this P-type resilient coating is formed between this luminescent layer and this source, hole.
7. Organnic electroluminescent device as claimed in claim 1, wherein this luminous zone comprises luminescent layer and N-type resilient coating, wherein this N-type resilient coating is formed between this luminescent layer and this electron source.
8. Organnic electroluminescent device as claimed in claim 1 wherein is sandwich construction in (1) this source, hole and comprise and contain NPB:F 4The layering of-TCNQ and contain F 4-TCNQ:WO 3The situation of layering under, this electron source is one or more layers structure, and this electron source contains lithium ion.
9. Organnic electroluminescent device as claimed in claim 1 wherein is sandwich construction and comprises and contain LiMn at (2) this electron source 2O 4Layering and contain under the situation of layering of BPhen:Li, this source, hole is one or more layers structure, and this source, hole comprises TCNQ.
10. Organnic electroluminescent device as claimed in claim 1 also comprises the LiF layer, and it is formed between this negative electrode and this electron source.
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